Fluorine-Containing Cyclic Compound, Fluorine-Containing Polymer Compound, Resist Material Using Same and Method for Forming Pattern

ABSTRACT

The present invention relates to, for example, a fluorine-containing cyclic compound represented by the following general formula (1). 
     
       
         
         
             
             
         
       
     
     In the general formula (1), R1a is a C 1 -C 25  cyclic alkyl group, cyclic alkenyl group or cyclic alkynyl group; each of R2 and R3 is independently a hydrogen atom, a halogen atom, or a C 1 -C 25  straight-chain, branched or cyclic alkyl group; and each of R1a, R2 and R3 may contain fluorine atom, oxygen atom, sulfur atom, nitrogen atom or an atomic group containing a carbon-carbon double bond.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of co-pending application Ser. No.10/589,807, filed Aug. 17, 2006, now U.S. Pat. No. ______, which is theU.S. national stage of international application no. PCT/JP2005/002400,filed Feb. 17, 2005. Priority is claimed based on Japanese patentapplication no. JP 2004-044142, filed Feb. 20, 2004.

TECHNICAL FIELD

The present invention relates to a novel fluorine-containing cycliccompound, a fluorine-containing polymer compound, a resist materialusing the same, and particularly to a chemically-amplified resistmaterial and a pattern forming method, of which researches have recentlyactively been conducted.

BACKGROUND OF THE INVENTION

In recent years, due to the development of digital equipment such ascomputer, the operation data to deal with and the throughput oftwo-dimensional and three-dimensional image data have become enormous.In order to quickly process such information, a large-volume, high-speedmemory and a high-performance microprocessor have become necessary.Furthermore, it is expected that a trend to broadband will beaccelerated and that the processing capacity required of digitalequipment will increase more and more, along with the development ofnetwork such as the Internet.

In order to accomplish this demand, many of device equipment, which arerepresented by semiconductor devices, are required to achieve furtherdensification and integration. In particular, the demand forphotolithography technique, which makes a fine processing possible, hasbecome stricter year by year. For producing a DRAM having a degree ofintegration of 1 G bits or greater, it is necessary to have a processingtechnique of the minimum line width of 0.13 micrometers or less. Inresponse to that, the utilization of a photolithography using ArFexcimer laser (193 nm) has started. Furthermore, the development ofphotolithography using F2 (157 nm) is going on for the purpose offorming fine patterns.

In these wavelength regions, novolac and polyvinyl phenol series resins,which have conventionally been used for resist materials, are too highin light absorption. Therefore, it is not possible to use them.Therefore, acrylic resins (see Patent Publication 1) and cycloolefinresins (see Patent Publication 2) have been examined. However, resinsthat are highly transparent at a wavelength of F2 (157 nm) are verylimited, and therefore advantage of fluororesins has become clear. Inparticular, there have been reports that fluorine-containing resistresins containing hydroxyl group have a characteristic that is alsosuperior in hydrophilicity, and therefore they are expected very much(Non-patent Publications 1 and 2).

The introduction of fluorine atom improves transparency in ultravioletregion, but at the same time it lowers etching resistance. In connectionwith polymerizability too, there remained many problems that monomers,in which fluorine atom and trifluoromethyl group are directly bonded toconventional norbornene rings, are low in polymerizability to lead tolow yield and are not capable of providing sufficient molecular weightsas materials. Therefore, functions that are achievable by these existingcompounds are not necessarily sufficient. There has been a desire for anovel monomer or its raw material that is capable of efficientlyproviding a further superior polymer.

On the other hand, epoxy resin and the like are used in the field ofsemiconductor device package, but there is used a method in which fineparticles of silicon oxide (SiO2) having a thermal expansion coefficientclose to that of a device substrate (Si substrate) are added to asealing resin material for the purpose of reducing thermal stress uponmounting onto a printed wiring board. However, in conventionaltechnique, a plastic package of conventional structure using epoxy resininferior to metal, ceramics, etc. in thermal conductivity is inferior inradiation characteristic and is quite high in thermal resistance.Therefore, it was disadvantageous in terms of a long-term reliability asan IC of high electric-power consumption such as power IC or as apackage of IC operating at high speed. Furthermore, fine particles ofSiO₂ added to resin to make it have low stress are very hard. Therefore,thermal stress generated upon mounting onto printed wiring board hasadded a large pressure locally to the device surface, thereby generatingdevice destruction. In other words, there has been a demand for amaterial that is high in heat resistance and hardly adds thermal stressto the device surface in the field of semiconductor package (see PatentPublication 3). In fact, it is difficult to satisfy the demandedperformances by a single semiconductor package material. Thus, variousprotecting films, etc. are used together. We can say that the packagematerial and the protecting film are integrated and achieve theirfunctions by compensating their respective weaknesses. A passivationfilm is used for preventing the intrusion of water and impurities intosemiconductor chip, and a buffer coating film is used for looseningstress concentration occurring in a package material. Hitherto,inorganic compounds such as silicon oxide have primarily been used forthin film materials, such as insulating film and protecting film, usedfor semiconductors. Nowadays, however, the usefulness of heat resistantpolymer materials such as polyimide have been recognized, and they areused for layer insulation film, passivation film, buffer coating film,etc. For the request of integration and high-speed of semiconductors inrecent years, there is a demand for a material corresponding to thehigh-speed transmission of signals. In high-speed transmission, thepropagation delay of signals becomes problematic, but it is effective tomake a material have a lower dielectric constant since the propagationdelay is proportional to relative dielectric constant of a material.Nowadays, it is known that fluororesins are low in dielectric constant,and fluorine-containing polyimide is also investigated as one ofpotential materials. A resin, into which fluorine atom has beenintroduced, has special properties possessed by fluorine, such as waterrepellency, non-adhesiveness, etc., and sometimes it can be utilized forthe aimed use. Sometimes, however, its utilization was difficult due toits specificity. Along with the appearance of new semiconductor appliedproducts in recent years, semiconductor packages have also beendiversified. There have been various demands for them to be morecompact, thinner, lower in dielectric constant, etc. A package materialsatisfying these has been demanded.

Patent Publication 1: Japanese Patent Laid-open Publication 10-161313Patent Publication 2: Japanese Patent Laid-open Publication 2000-89463Patent Publication 3: Japanese Patent Laid-open Publication 8-241913

Non-patent Publication 1: H. Ito, H. D. Truong, et al, J. Photopolym.Sci. Technol., 16, 523-536 (2003)Non-patent Publication 2: Francis Houlihan, Andrew Romano, Ralph R,Dammel, et al, J. Photopolym. Sci. Technol., 16, 581-590 (2003)

SUMMARY OF THE INVENTION

It is an object of the present invention to provide novelfluorine-containing cyclic compound and fluorine-containing polymercompound and to provide a resist material that has a high transparencyin a wide wavelength region from ultraviolet region to near-infraredregion and has a high adhesion to substrate, film-forming property andhigh etching resistance, and a pattern-forming method using the same. Itis another object of the present invention to provide a package materialfor semiconductor device.

As a result of a repeated eager examination to solve the above-mentionedtask, the present inventors have found a novel fluorine-containingcyclic compound having a cyclic structure such as norbornene ring and ahexafluoroisopropanol structure and have found that afluorine-containing polymer compound obtained by a polymerization orcopolymerization using this compound or a polymerizable monomer derivedfrom this compound has high transparency in a wide wavelength region,high adhesion to substrate, and film-forming property. Furthermore, wehave found that this fluorine-containing polymer compound has a highetching resistance derived from the cyclic structure and is effective asa resist material. Furthermore, we have found a pattern-forming methodusing this fluorine-containing polymer compound. On the other hand, wehave found that this fluorine-containing polymer compound is high inheat resistance due to having a cyclic structure in the molecule, issuperior in applicability due to a good solvent solubility derived fromhexafluoroisopropanol structure, and is superior in film-formingproperty and formability, thereby completing the present invention.Furthermore, in case that a semiconductor device is formed into apackage by using this fluorine-containing polymer compound itself or byadding hardener to this, we have found that stress to the devicesubstrate is very small and high credibility can be obtained.

DETAILED DESCRIPTION

The present invention provides novel fluorine-containing cyclic compoundand fluorine-containing polymer compound and provides a resist materialthat has a high transparency in a wide wavelength region fromultraviolet region to near-infrared region and has a high adhesion tosubstrate, film-forming property and high etching resistance, and apattern-forming method using the same. The fluorine-containing polymercompound is suitable as a package material for semiconductor device.

In the following, the present invention is described in detail. Thefluorine-containing cyclic compound represented by the general formula(1) or (2) of the present invention is a novel fluorine-containingcyclic compound having a cyclic structure such as norbornene ring and ahexafluoroisopropanol structure. In general, it is known that, as thefluorine content is increased, the improvement of transparency in a widewavelength region from ultraviolet region to near-infrared region andthe lowering of refractive index are induced. On the other hand, as thefluorine content is increased, lowering of adhesion to substrate andlowering of film-forming property are also induced. Therefore, it wasdifficult to achieve them together with high transparency and lowrefractive index. However, due to that a compound represented by thegeneral formula (1) or (2) has a hexafluoroisopropanol structure, apolymer compound derived from this became possible to have high adhesionto substrate and high film-forming property.

In a fluorine-containing cyclic compound represented by the generalformula (1) or (2) according to the present invention, R1a is a C₁-C₂₅cyclic alkyl group, cyclic alkenyl group or cyclic alkynyl group. Acyclic skeleton is preferable, since it contributes to etchingresistance that is necessary for resist material. A polycyclic skeletonis more preferably used, since it significantly contributes to etchingresistance. By introducing a cyclic structure into the molecule, itbecomes possible to increase glass transition temperature (Tg) of apolymer compound derived from this. By adjusting the proportion of thecyclic structure contained in the polymer compound, it becomes alsopossible to adjust Tg. Tg is an important element for the acid diffusionrate of a chemically amplified positive-type resist. It is an importantelement for reducing or adjusting thermal expansion coefficient in thefield of package material for semiconductor device and buffer coating.

On the other hand, in conventional fluorine-containing cyclic compounds,none of them was applied to resist materials and semiconductor packagematerials by leading it into polymer compounds.

R2 and R3 are not particularly limited as long as they do notsubstantially damage the properties of this compound. Each of them isindependently a hydrogen atom, a halogen atom, or a C₁-C₂₅straight-chain, branched or cyclic alkyl group. R1-R3 may containfluorine atom, oxygen atom, sulfur atom, nitrogen atom or an atomicgroup containing a carbon-carbon double bond.

A fluorine-containing cyclic compound represented by the general formula(3) according to the present invention is a polymerizable monomer thatcan be derived from the compound according to the above general formula(1) or (2). The advantageous effect by containing fluorine atom, theadvantageous effect by having a hexafluoroisopropanol structure, and theadvantageous effect by having a cyclic structure, particularly apolycyclic skeleton, are the same as those shown in connection with theabove general formula (1) or (2). That is, in the general formula (3),R1b is a C₁-C₂₅ cyclic alkyl group, cyclic alkenyl group, cyclic alkynylgroup, aryl group, or heterocyclic group, and may contain fluorine atom,oxygen atom, sulfur atom, nitrogen atom or an atomic group containing acarbon-carbon double bond. R2 to R7 are not particularly limited as longas they do not substantially damage the properties of this compound.Each of them is independently a hydrogen atom, a halogen atom, or aC₁-C₂₅ straight-chain, branched or cyclic alkyl group, and may containfluorine atom, oxygen atom, sulfur atom, nitrogen atom or an atomicgroup containing a carbon-carbon double bond. R8 is a carbonyl group ormethylene group, or a single bond.

A fluorine-containing cyclic compound represented by the general formula(4) or (5) according to the present invention is a polymerizable monomerthat can be derived from the compound according to the above generalformula (1) or (2). The advantageous effect by containing fluorine atom,the advantageous effect by having a hexafluoroisopropanol structure, andthe advantageous effect by having a cyclic structure, particularly apolycyclic skeleton, are the same as those shown in connection with theabove general formula (1) or (2). That is, in the general formula (4) or(5), R2, R3, R4 and R9 to R15 are not particularly limited as long asthey do not substantially damage the properties of this compound. Eachof them is independently a hydrogen atom, a halogen atom, or a C₁-C₂₅straight-chain, branched or cyclic alkyl group, and may contain fluorineatom, oxygen atom, sulfur atom, or nitrogen atom. R10 and R11 or R12 andR13 may be bonded together to form a ring. In such case, it is an C₁-C₂₅alkylene group that may contain a hetero atom such as oxygen, sulfur andnitrogen. “a” is 0 or 1, “b” is an integer of 0-2, and “c” is an integerof 0-2.

A fluorine-containing cyclic compound represented by the general formula(6) according to the present invention is a polymerizable monomer thatcan be derived from the compound according to the above general formula(4) or (5). The advantageous effect by containing fluorine atom, theadvantageous effect by having a hexafluoroisopropanol structure, and theadvantageous effect by having a cyclic structure, particularly apolycyclic skeleton, are the same as those shown in connection with theabove general formula (1) or (2). That is, in the general formula (6),R2 to R7 and R9 to R15 are not particularly limited as long as they donot substantially damage the properties of this compound. Each of themis independently a hydrogen atom, a halogen atom, or a C₁-C₂₅straight-chain, branched or cyclic alkyl group, and may contain fluorineatom, oxygen atom, sulfur atom, or nitrogen atom. R8 is a carbonyl groupor methylene group or a single bond. R10 and R11, R12 and R13, or R14and R15 may be bonded together to form a ring. In such case, it is anC₁-C₂₅ alkylene group that may contain a hetero atom such as oxygen,sulfur and nitrogen. “a” is 0 or 1, “b” is an integer of 0-2, and “c” isan integer of 0-2.

In a fluorine-containing cyclic compound represented by the generalformula (7) or (8) according to the present invention, the advantageouseffect by containing fluorine atom, the advantageous effect by having ahexafluoroisopropanol structure, and the advantageous effect by having acyclic structure, particularly a polycyclic skeleton, are the same asthose shown in connection with the above general formula (1) or (2).That is, R2, R3 and R4 are not particularly limited as long as they donot substantially damage the properties of this compound. Each of themis independently a hydrogen atom, a halogen atom, or a C₁-C₂₅straight-chain, branched or cyclic alkyl group, and may contain fluorineatom, oxygen atom, sulfur atom, or nitrogen atom.

A fluorine-containing cyclic compound represented by the general formula(9) according to the present invention is a polymerizable monomer thatcan be derived from the compound according to the above general formula(7) or (8). The advantageous effect by containing fluorine atom, theadvantageous effect by having a hexafluoroisopropanol structure, and theadvantageous effect by having a cyclic structure, particularly apolycyclic skeleton, are the same as those shown in connection with theabove general formula (1) or (2). That is, in the general formula (9),R2 to R7 are not particularly limited as long as they do notsubstantially damage the properties of this compound. Each of them isindependently a hydrogen atom, a halogen atom, or a C₁-C₂₅straight-chain, branched or cyclic alkyl group, and may contain fluorineatom, oxygen atom, sulfur atom, or nitrogen atom. R8 is a carbonyl groupor methylene group or a single bond.

A fluorine-containing polymer compound represented by the generalformula (10) according to the present invention is a polymer compoundobtained by polymerization in a manner to contain a polymerizablemonomer according to the general formula (3). The advantageous effect bycontaining fluorine atom, the advantageous effect by having ahexafluoroisopropanol structure, and the advantageous effect by having acyclic structure, particularly a polycyclic skeleton, are the same asthose shown in connection with the above general formula (1) or (2).That is, it is a fluorine-containing polymer compound having a weightaverage molecular weight of 1,000 to 1,000,000, which is characterizedin that it contains a repeating unit represented by the general formula(10). R1b and R2 to R8 are not particularly limited, as long as they donot substantially damage the properties of this compound, and are thesame as those shown in the general formula (3).

A fluorine-containing polymer compound represented by the generalformula (11) according to the present invention is a polymer compoundobtained by polymerization in a manner to contain a polymerizablemonomer according to the general formula (6). The advantageous effect bycontaining fluorine atom, the advantageous effect by having ahexafluoroisopropanol structure, and the advantageous effect by having acyclic structure, particularly a polycyclic skeleton, are the same asthose shown in connection with the above general formula (1) or (2).That is, it is a fluorine-containing polymer compound having a weightaverage molecular weight of 1,000 to 1,000,000, which is characterizedin that it contains a repeating unit represented by the general formula(11). If the molecular weight is less than this, it is not sufficient interms of mechanical strength and film-forming property. If the molecularweight is greater than this, it is not preferable in terms of solubilityin solvent and film-forming property. R2 to R15 are not particularlylimited, as long as they do not substantially damage the properties ofthis compound, and are the same as those shown in the general formula(6).

A fluorine-containing polymer compound represented by the generalformula (12) according to the present invention is a polymer compoundobtained by polymerization in a manner to contain a polymerizablemonomer according to the general formula (9). The advantageous effect bycontaining fluorine atom, the advantageous effect by having ahexafluoroisopropanol structure, and the advantageous effect by having acyclic structure, particularly a polycyclic skeleton, are the same asthose shown in connection with the above general formula (1) or (2).That is, it is a fluorine-containing polymer compound having a weightaverage molecular weight of 1,000 to 1,000,000, which is characterizedin that it contains a repeating unit represented by the general formula(12). If the molecular weight is less than this, it is not sufficient interms of mechanical strength and film-forming property. If the molecularweight is greater than this, it is not preferable in terms of solubilityin solvent and film-forming property. R2 to R8 are not particularlylimited, as long as they do not substantially damage the properties ofthis compound, and are the same as those shown in the general formula(9).

A fluorine-containing polymer compound represented by the generalformula (13) or (14) according to the present invention is a polymercompound obtained by polymerization in a manner to contain apolymerizable monomer according to the general formula (4) or (5). Theadvantageous effect by containing fluorine atom, the advantageous effectby having a hexafluoroisopropanol structure, and the advantageous effectby having a cyclic structure, particularly a polycyclic skeleton, arethe same as those shown in connection with the above general formula (1)or (2). That is, it is a fluorine-containing polymer compound having aweight average molecular weight of 1,000 to 1,000,000, which ischaracterized in that it contains a repeating unit represented by thegeneral formula (13) or (14). If the molecular weight is less than this,it is not sufficient in terms of mechanical strength and film-formingproperty. If the molecular weight is greater than this, it is notpreferable in terms of solubility in solvent and film-forming property.R2, R3, R4 and R9 to R15 are not particularly limited, as long as theydo not substantially damage the properties of this compound, and are thesame as those shown in the general formula (4) or (5).

A fluorine-containing polymer compound represented by the generalformula (15) or (16) according to the present invention is a polymercompound obtained by polymerization in a manner to contain apolymerizable monomer according to the general formula (7) or (8). Theadvantageous effect by containing fluorine atom, the advantageous effectby having a hexafluoroisopropanol structure, and the advantageous effectby having a cyclic structure, particularly a polycyclic skeleton, arethe same as those shown in connection with the above general formula (1)or (2). That is, it is a fluorine-containing polymer compound having aweight average molecular weight of 1,000 to 1,000,000, which ischaracterized in that it contains a repeating unit represented by thegeneral formula (15) or (16). If the molecular weight is less than this,it is not sufficient in terms of mechanical strength and film-formingproperty. If the molecular weight is greater than this, it is notpreferable in terms of solubility in solvent and film-forming property.R2, R3, and R4 are not particularly limited, as long as they do notsubstantially damage the properties of this compound, and are the sameas those shown in the general formula (7) or (8).

A fluorine-containing polymer compound, which is characterized in thatit contains a repeating unit represented by the general formula (17)according to the present invention, is a polymer compound obtained bypolymerization in a manner to contain a polymerizable monomer accordingto the general formulas (13) to (16) and an α-trifluoromethylacrylicester. A copolymer of the cyclic olefin and the α-trifluoromethylacrylicester becomes a material that is superior in heat resistance and high inmechanical strength and Tg, since it contains a cyclic structure in themain chain. It is also possible to adjust it to have necessaryproperties by changing the selection and the composition of the monomersto be combined in the copolymerization reaction. The advantageous effectby containing fluorine atom, the advantageous effect by having ahexafluoroisopropanol structure, and the advantageous effect by having acyclic structure, particularly a polycyclic skeleton, are the same asthose shown in connection with the above general formula (1) or (2).That is, it is a fluorine-containing polymer compound having a weightaverage molecular weight of 1,000 to 1,000,000, which is characterizedin that it contains a repeating unit represented by the general formula(17). If the molecular weight is less than this, it is not sufficient interms of mechanical strength and film-forming property. If the molecularweight is greater than this, it is not preferable in terms of solubilityin solvent and film-forming property. It is a hydrogen atom, or a C₁-C₂₅straight-chain, branched or cyclic alkyl group, and may contain fluorineatom, oxygen atom, sulfur atom, nitrogen atom, hydroxyl group orhexafluorocarbinol group.

A polymer compound according to the present invention, which ischaracterized in that it contains a repeating unit having an acid-labilegroup is a polymer compound obtained by polymerization in a manner tocontain a polymerizable monomer having an acid-labile group, or oneobtained by replacing a part of a polymer compound with an acid-labilegroup. As examples of the acid-labile group, they can be used withoutparticular limitation, as long as they are groups that generateselimination by the effect of photoacid generator, hydrolysis, etc. Asspecific examples are cited, it is possible to cite alkoxycarbonylgroup, acetal group, silyl group, acyl group, etc. The alkoxycarbonylgroup can be exemplified by tert-butoxycarbonyl group,tert-amyloxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group,i-propoxycarbonyl group and the like. As the acetal group, it ispossible to cite methoxymethyl group, ethoxyethyl group, butoxyethylgroup, cyclohexyloxyethyl group, benzyloxyethyl group, phenethyloxyethylgroup, ethoxypropyl group, benzyloxypropyl group, phenethyloxypropylgroup, ethoxybutyl group, ethoxyisobutyl group, etc. It is also possibleto use an acetal group in which a vinyl ether has been added to thehydroxy group. As the silyl group, it is possible to cite, for example,trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilylgroup, triethylsilyl group, i-propyldimethylsilyl group,methyldi-i-propylsilyl group, tri-i-propylsilyl group,t-butyldimethylsilyl group, methyldi-t-butylsilyl group,tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilylgroup, triphenylsilyl group, and the like. As the acyl group, it ispossible to cite acetyl group, propionyl group, butyryl group, heptanoylgroup, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group,lauryloyl group, myristoyl group, palmitoyl group, stearoyl group,oxalyl group, malonyl group, succinyl group, glutaryl group, adipoylgroup, piperoyl group, suberoyl group, azelaoyl group, sebacoyl group,acryloyl group, propioloyl group, methacryloyl group, crotonoyl group,oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group,campholoyl group, benzoyl group, phthaloyl group, isophthaloyl group,terephthaloyl group, naphthoyl group, toluoyl group, hydratoropoylgroup, atoropoyl group, cinnamoyl group, furoyl group, thenoyl group,nicotinoyl group, isonicotinoyl group, and the like. Furthermore, it isalso possible to use ones in which fluorine atoms have been substitutedfor a part or entirety of hydrogen atoms of these acid labile groups.

The purpose of using an acid labile group is to achieve positivephotosensitivity and dissolution in an alkali aqueous solution afterexposure to a high energy radiation such as a far infrared radiation ofa wavelength of 300 nm or shorter, excimer laser, X ray or the like, orelectron beam. One having fluorine atom at its functional group is forproviding transparency, and one having a cyclic structure is forproviding characteristics such as etching resistance and high glasstransition point. They can be used differently depending on the appliedfields of the present invention.

In the fluorine-containing cyclic compound and the fluorine-containingpolymer compound of the present invention, it is possible to protect apart or the entirety of the hydroxyl groups, which are contained in themolecule, with a protecting group. It is possible to change and adjustpolarity of the molecule by changing the type of the protecting group orthe degree of protection. With this, it is possible to make solubilityin solvent, applicability to substrate, surface tension, dispersibilityof photoacid generator, acid diffusion rate, etc. appropriate. Theprotecting group is a C₁-C₂₅ straight-chain, branched or cyclichydrocarbon group or aromatic hydrocarbon group. It can be exemplifiedby methyl group, ethyl group, propyl group, isopropyl group, cyclopropylgroup, n-propyl group, iso-propyl group, sec-butyl group, tert-butylgroup, n-pentyl group, cyclopentyl group, sec-pentyl group, neopentylgroup, hexyl group, cyclohexyl group, ethylhexyl group, norbornel group,adamantyl group, vinyl group, allyl group, butenyl group, pentenylgroup, ethynyl group, phenyl group, benzyl group, 4-methoxybenzyl groupand the like. They may be ones in which a part or the entirety of theabove functional groups has been replaced with fluorine atoms. As thosecontaining oxygen atom, it is possible to cite alkoxycarbonyl group,acetal group, acyl group and the like. The alkoxycarbonyl group can beexemplified by tert-butoxycarbonyl group, tert-amyloxycarbonyl group,methoxycarbonyl group, ethoxycarbonyl group, i-propoxycarbonyl group andthe like. As the acetal group, there are cited acyclic ethers, such asmethoxymethyl group, methoxyethoxymethyl group, ethoxyethyl group,butoxyethyl group, cyclohexyloxyethyl group, benzyloxyethyl group,phenethyloxyethyl group, ethoxypropyl group, benzyloxypropyl group,phenethyloxypropyl group, ethoxybutyl group and ethoxyisobutyl group,and cyclic ethers, such as tetrahydrofuranyl group and tetrahydropyranylgroup. As the acyl group, it is possible to cite acetyl group, propionylgroup, butyryl group, heptanoyl group, hexanoyl group, valeryl group,pivaloyl group, isovaleryl group, lauryloyl group, myristoyl group,palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinylgroup, glutaryl group, adipoyl group, piperoyl group, suberoyl group,azelaoyl group, sebacoyl group, acryloyl group, propioloyl group,methacryloyl group, crotonoyl group, oleoyl group, maleoyl group,fumaroyl group, mesaconoyl group, campholoyl group, benzoyl group,phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoylgroup, toluoyl group, hydratoropoyl group, atoropoyl group, cinnamoylgroup, furoyl group, thenoyl group, nicotinoyl group, isonicotinoylgroup, and the like. Furthermore, it is also possible to use ones inwhich fluorine atoms have been substituted for a part or entirety ofhydrogen atoms of the above substituents.

It is also possible to introduce an acid-labile protecting group intothe hydroxyl group. It is preferably used as a method for adjustingsolubility before and after the exposure in the case of the use forresist. In particular, hexafluoroisopropanol group is an acid hydroxylgroup and functions as a soluble group to an alkali developing solution.In other words, it is possible to make it function as a positive-typeresist that makes alkali development possible by protecting thehexafluoroisopropanol group in the molecule with an acid-labileprotecting group, followed by mixing with a photoacid generator toproduce a resist and then exposing this.

The fluorine-containing cyclic compound and the fluorine-containingpolymer compound of the present invention are effective in a resistmaterial of any type such as positive type, negative type and chemicallyamplified type. In each use, it can be used by changing its mixingamount and mixing method.

A fluorine-containing polymer compound of the present invention is oneprepared by homopolymerization of a fluorine-containing cyclic compoundrepresented by the general formulas (1) to (9) or by copolymerizationwith another in a manner to contain it. They are those represented bythe general formulas (10) to (17), a fluorine-containing polymercompound of any of the general formulas (10) to (17), which ischaracterized in that it contains a repeating unit having an acid-labilegroup, and a fluorine-containing polymer compound of any of the generalformulas (10) to (17), which is characterized in that the hydroxylgroups contained in the molecule are partially or entirely protectedwith protecting groups.

As a monomer that can be copolymerized with the fluorine-containingcyclic compound of the present invention is specifically exemplified, itis preferable to conduct a copolymerization with at least one monomerselected from at least maleic anhydride, acrylic esters,fluorine-containing acrylic esters, methacrylic esters,fluorine-containing methacrylic esters, styrene compounds,fluorine-containing styrene compounds, vinyl ethers, fluorine-containingvinyl ethers, allyl ethers, fluorine-containing allyl ethers, olefins,fluorine-containing olefins, norbornene compounds, fluorine-containingnorbornene compounds, sulfur dioxide, and vinyl silane.

The polymerization method of a polymer compound according to the presentinvention is not particularly limited, as long as it is a generally usedmethod. Radical polymerization, ionic polymerization and the like arepreferable. In some cases, it is possible to use coordinated anionicpolymerization, living anionic polymerization, cationic polymerization,ring-opening metathesis polymerization, vinylene polymerization, vinyladdition and the like.

The radical polymerization may be conducted by a known polymerizationmethod, such as bulk polymerization, solution polymerization, suspensionpolymerization or emulsion polymerization, in the presence of a radicalpolymerization initiator or radical initiating source, with abatch-wise, half-continuous or continuous operation.

The radical polymerization initiator is not particularly limited. As itsexamples, azo compounds, peroxide compounds and redox compounds arecited. In particular, azobisbutyronitrile, t-butylperoxypivalate,di-t-butylperoxide, i-butyrylperoxide, lauroylperoxide, succinic acidperoxide, dicinnamylperoxide, di-n-propylperoxydicarbonate,t-butylperoxyallyl monocarbonate, benzoyl peroxide, hydrogen peroxide,ammonium persulfate, and like are preferable.

The reaction vessel used in the polymerization reaction is notparticularly limited. Furthermore, a polymerization solvent may be usedin the polymerization reaction. As the polymerization solvent, one thatdoes not interfere with the radical polymerization is preferable.Representative ones are ester solvents such as ethyl acetate and n-butylacetate; ketone solvents such as acetone and methyl isobutyl ketone;hydrocarbon solvents such as toluene and cyclohexane; and alcoholsolvents such as methanol, isopropyl alcohol and ethylene glycolmonomethyl ether. Furthermore, it is also possible to use solvents suchas water, ethers, cyclic ethers, fluorohydrocarbons, and aromatics.These solvents can be used singly or in combination of at least twotypes. Furthermore, it may be accompanied in use with a molecular weightadjusting agent such as mercaptan. The reaction temperature of thecopolymerization reaction is suitably changed depending on the radicalpolymerization initiator or radical polymerization initiating source. Ingeneral, 20-200° C. is preferable. In particular, 30-140° C. ispreferable.

On the other hand, the ring-opening metathesis polymerization can beconducted by a known method using a transition metal catalyst in thepresence of a cocatalyst.

The polymerization catalyst is not particularly limited. As theexamples, Ti, V, Mo and W catalysts are cited. In particular, titaniumchloride, vanadium chloride, vanadium trisacetylacetonato, vanadiumbisacetylacetonatodichloride, molybdenum chloride, and tungsten chlorideand the like are preferable. The amount of the catalyst is from 10 mol %to 0.001 mol %, preferably 1 mol % to 0.01 mol %, relative to the usedmonomer.

As the cocatalyst, alkylaluminum, alkyltin and the like are cited. Inparticular, it can be exemplified by aluminum-based ones such astrialkylaluminums such as trimethylaluminum, triethylaluminum,tripropylaluminum, triisopropylaluminum, triisobutylaluminum,tri-2-methylbutylaluminum, tri-3-methylbutylaluminum,tri-2-methylpentylaluminum, tri-3-methylpentylaluminum,tri-4-methylpentylaluminum, tri-2-methylhexylaluminum,tri-3-methylhexylaluminum, and trioctylaluminum; dialkylaluminum halidesdimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminumchloride, and diisobutylaluminumchloride; monoalkylaluminum halides suchas methylaluminum dichloride, ethylaluminum dichloride, ethylaluminumdiiodide, propylaluminum dichloride, isopropylaluminum dichloride,butylaluminum dichloride, and isobutylaluminum dichloride; andalkylaluminum sesquichlorides such as methylaluminum sesquichloride,ethylaluminum sesquichloride, propylaluminum sesquichloride; andisobutylaluminum sesquichloride; tetra-n-butyltin, tetraphenyltin, andtriphenylchlorotin. The amount of the cocatalyst is by molar ratio 100equivalents or less, preferably 30 equivalents or less, relative to thetransition metal catalyst.

The polymerization solvent will do, as long as it does not interferewith the polymerization. As its representative ones, it can beexemplified by aromatic hydrocarbons such as benzene, toluene, xylene,chlorobenzene and dichlorobenzene; hydrocarbons such as hexane, heptaneand cyclohexane; and halogenated hydrocarbons such as carbontetrachloride, chloroform, methylene chloride and 1,2-dichloroethane.These solvents may be used alone or in a mixture of at leas two kinds.The reaction temperature is generally preferably −70° C. to 200° C.,particularly preferably −30° C. to 60° C.

The vinylene polymerization can be conducted by a known process in thepresence of a cocatalyst using a transition metal catalyst, such asiron, nickel, rhodium, palladium and platinum, or a metal catalyst, suchas zirconium, titanium, vanadium, chromium, molybdenum, and tungsten.

The polymerization catalyst is not particularly limited. As examples,particularly, there are preferable transition metal compounds such asiron(II) chloride, iron(III) chloride, iron(II) bromide, iron(III)bromide, iron(II) acetate, iron(III) acetylacetate, ferrocene,nickelocene, nickel(II) acetate, nickel bromide, nickel chloride,dichlorohexylnickel acetate, nickel lactate, nickel oxide, nickeltetrafluoroborate, bis(allyl)nickel, bis(cyclopentadienyl)nickel,nickel(II) hexafluoroacetylacetonatotetrahydrate, nickel(II)trifluoroacetylacetonatodihydrate, nickel(II)acetylacetonatotetrahydrate, rhodium(III) chloride, rhodiumtris(triphenylphosphine)trichloride, palladium(II)bis(trifluoroacetate), palladium(II) bis(acetylacetonato), palladium(II)2-ethylhexanoate, palladium(II) bromide, palladium(II) chloride,palladium(II) iodide, palladium(II) oxide,monoacetonitriletris(triphenylphosphine)palladium(II) tetrafluoroborate,tetrakis(acetonitrile)palladium(II) tetrafluoroborate,dichlorobis(acetonitrile)palladium(II),dichlorobis(triphenylphosphine)palladium(II),dichlorobis(benzonitrile)palladium(II), palladium acetylacetonato,palladium bis(acetonitrile)dichloride, palladiumbis(dimethylsulfoxide)dichloride and platinumbis(triethylphosphine)hydrobromide, and transition metal compounds suchas vanadium(IV) chloride, vanadium trisacetylacetonato, vanadiumbisacetylacetonatodichloride,trimethoxy(pentamethylcyclopentadienyl)titanium(IV),bis(cyclopentadienyl)titanium dichloride, andbis(cyclopentadienyl)zirconium dichloride. The catalyst amount is from10 mol % to 0.001 mol %, preferably from 1 mol % to 0.01 mol %, relativeto the used monomer.

As the cocatalyst, alkylaluminoxane, alkylaluminum and the like arecited. In particular, it can be exemplified by methylaluminoxane (MAO),trialkylaluminums such as trimethylaluminum, triethylaluminum,tripropylaluminum, triisopropylaluminum, triisobutylaluminum,tri-2-methylbutylaluminum, tri-3-methylbutylaluminum,tri-2-methylpentylaluminum, tri-3-methylpentylaluminum,tri-4-methylpentylaluminum, tri-2-methylhexylaluminum,tri-3-methylhexylaluminum, and trioctylaluminum; dialkylaluminum halidessuch as dimethylaluminum chloride, diethylaluminum chloride,diisopropylaluminum chloride, and diisobutylaluminum chloride;monoalkylaluminum halides such as methylaluminum dichloride,ethylaluminum dichloride, ethylaluminum diiodide, propylaluminumdichloride, isopropylaluminum dichloride, butylaluminum dichloride, andisobutylaluminum dichloride; and alkylaluminum sesquichlorides such asmethylaluminum sesquichloride, ethylaluminum sesquichloride,propylaluminum sesquichloride, and isobutylaluminum sesquichloride. Theamount of the cocatalyst is 50 to 500 equivalents in terms of Alconversion in the case of methylaluminoxane. In the case of otheralkylaluminums, it is 100 equivalents or less, preferably 30 equivalentsor less, relative to the transition metal catalyst by molar ratio.

The polymerization solvent will do as long as it does not interfere withthe polymerization. As representative ones, it can be exemplified byaromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene,and dichlorobenzene; hydrocarbons such as hexane, heptane, andcyclohexane; halogenated hydrocarbons such as carbon tetrachloride,chloroform, methylene chloride, and 1,2-dichloroethane;dimethylformamide, N-methylpyrolidone, and N-cyclohexylpyrolidone. Thesesolvents may be used alone or in a mixture of at least two kinds. Thereaction temperature is generally preferably −70° C. to 200° C.,particularly preferably −40° C. to 80° C.

As a process of removing an organic solvent or water from the obtainedsolution or dispersion of the polymer compound according to the presentinvention, a process such as reprecipitation, filtration or heateddistillation under reduced pressure is possible.

As a process of forming a fluorine-containing polymer compound accordingto the present invention into a thin film, for example, it is possibleto use a process in which it is dissolved in an organic solvent,followed by application and drying. The organic solvent to be used isnot particularly limited, as long as the polymer compound is soluble. Itis possible to use ketones such as acetone, methyl ethyl ketone,cyclohexanone, methyl isoamyl ketone and 2-heptanone; polyhydricalcohols such as ethylene glycol, ethylene glycol monoacetate,diethylene glycol, diethylene glycol monoacetate, propylene glycol,propylene glycol monoacetate, dipropylene glycol, or monomethyl ether,monoethyl ether, monopropyl ether, monobutyl ether or monophenyl etherof dipropylene glycol monoacetate, and their derivatives; cyclic etherssuch as dioxane; esters such as methyl lactate, ethyl lactate, methylacetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate,methyl methoxypropionate, and ethyl ethoxypropionate; aromatic solventssuch as xylene and toluene; fluorine-series solvents such as fleon,alternative fleon, perfluoro compounds, and hexafluoroisopropyl alcohol;and terpene-based petroleum naphtha solvents and paraffinic solvents,which are high-boiling-point, weak solvents, for the purpose ofincreasing applicability. These may be used singly or in a mixture of atleast two kinds.

A resist composition according to the present invention is onecontaining a dissolution inhibitor, of which solubility in alkaliaqueous solution changes by the action of acid, and the polymer compoundor one in which a dissolution inhibitor is built in the polymercompound. These are particularly suitable as positive-type resistmaterials. They are also suitable as positive-type resists for 248 nmKrF or 193 nm ArF excimer laser or vacuum ultraviolet (typically 157 nm)region F₂ laser, electron beam resists, and resists for X-ray, whichcorrespond to a recent trend for finer semiconductors. In other words,the dissolution inhibitor, of which solubility in alkali aqueoussolution changes by the action of acid, is such that at least one ofhexafluorocarbinol groups becomes an acid-labile group. It can be usedwithout a particular limitation in its structure. General acid-labilegroups are the above-mentioned acid-labile groups, and they arefunctional groups that are severed by acids. The polymer compound usingsuch dissolution inhibitor is insoluble or scarcely soluble in alkaliaqueous solution prior to the activating energy ray irradiation. It ishydrolyzed by an acid generated from a photoacid generator by theactivating energy ray irradiation and thereby shows solubility in alkaliaqueous solution.

The photoacid generator used in the resist material of the presentinvention is not particularly limited, and an arbitrary one can beselected from those used as acid generators of chemically amplifiedresists and then used. As examples of such photoacid generators, thereare cited bissulfonyldiazomethanes, nitrobenzyl derivatives, oniumsalts, halogen-containing triazine compounds, cyano group-containingoximesulfonate compounds, and other oximesulfonate compounds. Thesephotoacid generators may be used singly or in a combination of at leasttwo kinds. Its content is generally selected in a range of 0.5 to 20parts by weight relative to 100 parts by weight of the polymer compound.If this amount is less than 0.5 parts by weight, image formationcapability is insufficient. If it exceeds 20 parts by weight, it isdifficult to form a homogeneous solution. With this, storage stabilitytends to be lowered.

A conventional resist pattern forming method can be used as a method forusing the resist material of the present invention. That is, firstly asolution of the resist material is applied to a substrate such assilicon wafer with a spinner, followed by drying to form aphotosensitive layer. This is exposed to a high-energy ray by anexposure apparatus or the like through a desired mask pattern, followedby heating. Then, this is subjected to a development treatment using adeveloping solution, for example, an alkali aqueous solution such as0.1-10 wt % tetramethylammonium hydroxide aqueous solution. This formingmethod makes it possible to obtain a pattern conforming to the maskpattern. Furthermore, according to need, it is possible to containadditives that are miscible with the resist material, for example,various additives such as additional resins, quencher, plasticizer,stabilizer, coloring agent, surfactant, tackifier, leveling agent,deforming agent, compatibility enhancing agent, adhesion enhancingagent, and antioxidant.

A high-energy ray used in the present invention is not particularlylimited. In particular, in the case of conducting a fine processing, itis effective to use an exposure device equipped with a short-wavelengthhigh-energy ray (e.g., F₂ excimer laser, ArF excimer laser, KrF excimerlaser, or soft X-ray) generating source. It is effective to use animmersion exposure device that makes it possible to conduct a moreefficient fine processing in numerical aperture and effective wavelengthby using a medium (e.g., water and fluorine-containing solvents), intowhich the used high-energy ray has a less absorption, at a part of theoptical path. The present resist material is also preferable in the caseof use in this device.

Fluorine-containing polymer compounds represented by the generalformulas (10) to (17), fluorine-containing polymer compounds representedby the general formulas (10) to (17), which are characterized incontaining a repeating unit having an acid-labile group, andfluorine-containing polymer compounds represented by the generalformulas (10) to (17), which are characterized in that a part orentirety of the hydroxyl groups contained in the molecule is protectedwith a protecting group, can preferably be used as semiconductor devicepackage materials. Sealing material and overcoat material arerepresentative as semiconductor device package materials. Buffer coatfilm, passivation film and their protecting film are representative asovercoat materials. The fluorine-containing polymer compound of thepresent invention is high in heat resistance due to having a cyclicstructure in the molecule, is superior in applicability due to a goodsolvent solubility derived from hexafluoroisopropanol structure, and issuperior in film-forming property and formability. It is possible toobtain characteristics suitable to each use by the type of thesubstituent contained in the molecule, the type of the monomer to becopolymerized, its composition, the compounding ratio to anothermaterial to be mixed with, the type of the hardener, etc.

In the fluorine-containing polymer compound according to the presentinvention, a preferable molecular weight as a semiconductor devicepackage material is in a range of Mw 1,000-1,000,000, preferably Mw10,000-500,000. If the molecular weight is excessively small, sealingmaterial and protecting film become low in mechanical strength,resulting in growing tendency to generate defects. If the molecularweight is excessively large, solvent solubility becomes low, andfilm-forming property and formability become low, thereby notsufficiently achieving the original capabilities of the material. For asemiconductor device package material, Tg of at least 100° C. isnecessary, preferably 150° C. or higher, more preferably 200° C. orhigher. To make it have a higher Tg, it is effective to subject afluorine-containing polymer compound of the present invention togetherwith hardener to heat treatment or light irradiation to form across-linked structure. As the hardener, there are cited organicperoxide, isocyanate, melamine, epoxy compound, polyamine, acidanhydride, and polyhydric phenol. It is preferable to use a combinationwith curing catalyst, curing assistant, reactive diluent, cross-linkingagent or chain extension agent. Curing method is not particularlylimited. It is possible to use a known method such as heat, light orradioactive ray. For example, in the case of conducting a sealing ofsemiconductor, it is preferable to use a curing by heat rather thanlight from the viewpoint of light transparency. It is possible andpreferable to use a blend with filler or another resin for the purposeof improving chemical, mechanical or electrical characteristics. As amethod for packaging a semiconductor device, it is possible to use aknown method, and it is not particularly limited. For example, there arecited sealing by transfer molding method, sealing by potting method, andthin film forming methods such as spin coating, roll coating anddipping.

In the following, embodiments of the present invention are specificallydescribed by examples, but the present invention is not limited to theseexamples.

Example 1 Synthesis of Compound 2

A 50 ml autoclave made of SUS was charged with 2-acetyl-5-norbornene 1(37.0 g) and concentrated sulfuric acid (0.17 g), followed by sealing.Hexafluoroacetone (65.0 g) was weighed and put into this, followed byheating in an oil bath of 60° C. and stirring for 23 hr. After thereaction, the autoclave was cooled down, followed by adding saturatedsodium bicarbonate aqueous solution to the contents and then extractionby adding toluene. The organic phase was washed with saturated brine,followed by concentration and then vacuum distillation, therebyobtaining 23.4 g of a colorless, transparent liquid. This was analyzedby infrared absorption spectrum (IR), nuclear magnetic resonancespectrum (NMR) and a gas chromatograph mass spectrometer (GC-MS). As aresult, it was a mixture of two isomers (Isomer 1 and Isomer 2) of thecompound 2. An isomer ratio of Isomer 1 to Isomer 2 was 75:25.

Property Data Compound 2

IR (cm-1): (a mixture of Isomers 1 and 2): 3294, 3069, 2979, 2947, 2877,1697, 1448, 1273, 1240, 1198, 1164, 1149, 1099, 1033, 979, 709, 636

¹H-NMR (TMS, CDCl3): (Isomer 1): 1.36 (m, 1H), 1.52 (m, 2H), 1.83 (m,1H), 2.94 (q, 2H), 2.97 (brs, 1H), 3.14 (m, 1H), 3.28 (brs, 1H), 5.84(dd, 1H), 6.22 (dd, 1H), 6.99 (s, 1H),

(Isomer 2): 1.31 (m, 1H), 1.52 (m, 2H), 1.95 (m, 1H), 2.97 (brs, 1H),3.00 (brs, 1H), 3.06 (brs, 1H), 3.14 (m, 1H), 6.14 (dd, 1H), 6.22 (dd,1H), 7.05 (s, 1H)

¹⁹F-NMR (CFCl3, CDCl3): (Isomer 1): −78.82 (q, 3H), −78.63 (q, 3H),(Isomer 2): −78.82 (q, 3H), −78.63 (q, 3H)

GC-MS (EI): (Isomer 1): m/e 302 (M+), 237, 217, (Isomer 2): m/e 302(M+), 237, 217

Example 2 Synthesis of Compound 3

A 100 ml round-bottom flask equipped with a reflux condenser and astirrer was charged with the compound 2 (5.2 g) and ethyl alcohol (25ml), followed by adding NaBH4 (0.3 g) with stirring at room temperatureand then stirring at room temperature for 30 min. After the reaction,the contents were added to diluted hydrochloric acid (100 ml), followedby adding diisopropyl ether (200 ml) to this to conduct extraction. Itwas separated into two layers, and the organic layer was taken, followedby washing with saturated sodium bicarbonate aqueous solution andsaturated brine. The obtained solution was concentrated, followed byrecrystallization with n-heptane, thereby obtaining white-color crystals(2.2 g). This was analyzed by infrared absorption spectrum (IR), nuclearmagnetic resonance spectrum (NMR) and a gas chromatograph massspectrometer (GC-MS). As a result, it was a mixture of four isomers(Isomers 1-4) of the compound 3. An isomer ratio of Isomer 1:Isomer2:Isomer 3:Isomer 4 was 64:19:11:6.

Property Data Compound 3

IR (cm-1): (a mixture of Isomers 1, 2, 3 and 4): 3425, 3068, 2979, 2933,2908, 2868, 1314, 1281, 1225, 1202, 1166, 1151, 1140, 1052, 1042, 1004,979, 719

¹H-NMR (TMS, CDCl3): (Isomer 1): 0.52 (m, 1H), 1.28-1.53 (m, 2H),1.83-2.39 (m, 5H), 2.60-2.99 (m, 2H), 3.61 (t, 1H), 6.01 (dd, 1H), 6.22(s, 1H), 6.27 (dd, 1H), (Isomer 2): 0.93 (m, 1H), 1.28-1.53 (m, 2H),1.83-2.39 (m, 5H), 2.60-2.99 (m, 2H), 3.71 (t, 1H), 5.91 (dd, 1H), 6.13(s, 1H), 6.27 (dd, 1H), (Isomer 3): 0.52 (m, 1H), 1.28-1.53 (m, 2H),1.83-2.39 (m, 5H), 2.60-2.99 (m, 2H), 4.05 (t, 1H), 6.11 (dd, 1H), 6.27(s, 1H), 6.27 (dd, 1H), (Isomer 4): 1.03 (m, 1H), 1.28-1.53 (m, 2H),1.83-2.39 (m, 5H), 2.60-2.99 (m, 2H), 3.95 (t, 1H), 6.27 (s, 1H), 6.27(m, 2H)

¹⁹F-NMR (CFCl3, CDCl3): (a mixture of Isomers 1, 2, 3 and 4): −80.01 (q,3H), −76.08 (q, 3H)

GC-MS (EI): (Isomer 1): m/e 304 (M+), 286 (—H2O), 267 (—H2O, —F), 237,(Isomer 2): m/e 304 (M+), 286 (—H2O), 267 (—H2O, —F), 237, (Isomer 3):m/e 304 (M+), 286 (—H2O), 267 (—H2O, —F), 237, (Isomer 4): m/e 304 (M+),286 (—H2O), 267 (—H2O, —F), 237

Example 3 Synthesis of Compound 4

A 100 ml round-bottom flask equipped with a reflux condenser and astirrer was charged with 2-acetyl-5-norbornene 1 (64 g), a catalyst (3.4g) having 5 wt % palladium carried on activated carbon, and methylalcohol (200 ml). The inside of the flask was turned into hydrogenatmosphere, followed by stirring at room temperature for 14 hours. Afterthe reaction, the contents were filtered by Celite, and the filtrate wassubjected to vacuum distillation, thereby obtaining the compound 4 (53.3g).

Example 4 Synthesis of Compound 5

A 50 ml autoclave made of SUS was charged with the compound 4 (50.0 g)and concentrated sulfuric acid (0.41 g), followed by sealing.Hexafluoroacetone (73.0 g) was weighed and put into this, followed byheating in an oil bath of 60° C. and stirring for 41 hr. After thereaction, the autoclave was cooled down, followed by adding the contentsto saturated sodium bicarbonate aqueous solution and then extraction byadding diisopropyl ether (200 ml). It was separated into two layers, andthe organic layer was taken, followed by washing with saturated brine.The obtained solution was concentrated, followed by vacuum distillation,thereby obtaining a colorless, transparent liquid (92.4 g). This wasanalyzed by infrared absorption spectrum (IR), nuclear magneticresonance spectrum (NMR) and a gas chromatograph mass spectrometer(GC-MS). As a result, it was a mixture of two isomers (Isomer 1 andIsomer 2) of the compound 5. An isomer ratio of Isomer 1 to Isomer 2 was70:30.

Property Data Compound 5

IR (cm-1): (a mixture of Isomers 1 and 2): 3301, 2960, 2877, 1696, 1455,1367, 1322, 1273, 1238, 1194, 1163, 1027, 977, 719, 697, 651

¹H-NMR (CDCl3): (Isomer 1): 1.10-1.70 (m, 7H), 1.91 (m, 1H), 2.35 (t,1H), 2.50 (m, 2H), 2.91 (d, 1H), 3.01 (d, 1H), 7.07 (s, 1H), (Isomer 2):1.10-1.70 (m, 7H), 1.73 (m, 1H), 2.32 (t, 1H), 2.65 (t, 1H), 2.81 (d,1H), 2.95 (m, 1H), 3.01 (d, 1H), 7.06 (s, 1H)

¹⁹F-NMR (CFCl3, CDCl3): (Isomer 1): −78.82 (q, 3H), −78.65 (q, 3H),(Isomer 2): −79.07 (q, 3H), −78.49 (q, 3H)

GC-MS (EI): (Isomer 1): m/e 304 (M+), 286 (—H2O), 263, 237, (Isomer 2):m/e 304 (M+), 286 (—H2O), 263, 237

Example 5 Synthesis of Compound 6

A 1,000 ml autoclave made of SUS was charged with the compound 5 (91.0g), a catalyst (9.1 g) having 5 wt % ruthenium carried on activatedcarbon, and diisopropyl ether (300 ml), followed by sealing. The insideof the autoclave was depressurized, followed by heating in an oil bathof 100° C. Then, hydrogen was introduced into the autoclave. Stirringwas continued for 14 hours, while adjusting the amount of hydrogenintroduced in a manner that the pressure inside of the autoclave isalways set to 0.7-1.0 MPa. After the reaction, the contents werefiltered by Celite, and the filtrate was concentrated. This wasrecrystallized by n-heptane, thereby obtaining white-color crystals(82.7 g). This was analyzed by infrared absorption spectrum (IR),nuclear magnetic resonance spectrum (NMR) and a gas chromatograph massspectrometer (GC-MS). As a result, it was a mixture of four isomers(Isomers 1-4) of the compound 6. An isomer ratio of Isomer 1:Isomer2:Isomer 3:Isomer 4 was 37:36:17:10.

Property Data Compound 6

IR (cm-1): (a mixture of Isomers 1, 2, 3 and 4): 3448, 3093, 2958, 2915,2867, 1457, 1281, 1227, 1204, 1162, 1152, 1138, 1051, 1019, 994, 930,850, 716, 671

¹H-NMR (CDCl3): (Isomer 1): 0.90-2.42 (m, 14H), 3.89 (t, 1H), 6.33 (s,1H), (Isomer 2): 0.90-2.42 (m, 14H), 3.75 (t, 1H), 6.33 (s, 1H), (Isomer3): 0.90-2.42 (m, 14H), 4.00 (t, 1H), 6.29 (s, 1H), (Isomer 4):0.90-2.42 (m, 14H), 4.03 (t, 1H), 6.44 (s, 1H)

¹⁹F-NMR (CFCl3, CDCl3): (Isomer 1): −79.98 (q, 3H), −76.08 (q, 3H),(Isomer 2): −80.00 (q, 3H), −75.99 (q, 3H), (Isomer 3): −80.00 (q, 3H),−76.02 (q, 3H), (Isomer 4): −79.93 (q, 3H), −75.99 (q, 3H)

GC-MS (EI): (Isomer 1): m/e 306 (M+), 288 (—H2O), 260, 237), (Isomer 2):m/e 306 (M+), 288 (—H2O), 260, 237, (Isomer 3): m/e 306 (M+), 305, 288(—H2O), 260, 237, (Isomer 4): m/e 306 (M+), 304, 288 (—H2O), 259, 246

Example 6 Synthesis of Compound 7

A 1,000 ml round-bottom flask equipped with a reflux condenser and astirrer was charged with the compound 6 (64.9 g), methacrylic anhydride(36.0 g), methanesulfonic acid (5.3 g), and toluene (325 ml). This washeated in an oil bath of 90° C., and stirring was conducted for 3 hours.After the reaction, the reaction solution was added to saturated sodiumbicarbonate aqueous solution, followed by adding 500 ml of toluene toconduct extraction. It was separated into two layers, and the organiclayer was taken, followed by washing with saturated brine and thenadding phenothiazine (0.33 g). The obtained solution was concentrated,followed by vacuum distillation, thereby obtaining 63.2 g of acolorless, transparent liquid. This was analyzed by infrared absorptionspectrum (IR), nuclear magnetic resonance spectrum (NMR) and a gaschromatograph mass spectrometer (GC-MS). As a result, it was a mixtureof four isomers of the compound 7. An isomer ratio of Isomer 1:Isomer2:Isomer 3:Isomer 4 was 38:34:17:11

Property Data Compound 7

IR (cm-1): (a mixture of Isomers 1, 2, 3 and 4): 3301, 2955, 2874, 1688,2634, 1455, 1203, 1171, 1143, 1050, 1022, 1009, 946, 815, 715, 660

¹H-NMR (CDCl3): (Isomer 1): 0.75-1.55 (m, 8H), 1.75 (m, 1H), 1.95 (t,3H), 2.09-2.45 (m, 4H), 4.91 (m, 1H), 5.67 (m, 1H), 6.18 (m, 1H), 6.21(s, 1H), (Isomer 2): 0.75-1.55 (m, 8H), 1.75 (m, 1H), 1.97 (t, 3H),2.09-2.45 (m, 4H), 4.82 (m, 1H), 5.57 (s, 1H), 5.67 (m, 1H), 6.18 (m,1H), (Isomer 3): 0.75-1.55 (m, 8H), 1.75 (m, 1H), 1.96 (t, 3H),2.09-2.45 (m, 4H), 4.98 (m, 1H), 5.67 (m, 1H), 6.05 (s, 1H), 6.18 (m,1H), (Isomer 4): 0.75-1.55 (m, 8H), 1.75 (m, 1H), 1.96 (t, 3H),2.09-2.45 (m, 4H), 5.11 (m, 1H), 5.67 (m, 1H), 5.80 (s, 1H), 6.18 (m,1H)

¹⁹F-NMR (CFCl3, CDCl3): (Isomer 1): −79.29 (q, 3H), −77.00 (q, 3H),(Isomer 2): −79.09 (q, 3H), −77.14 (q, 3H), (Isomer 3): −79.00 (q, 3H),−77.34 (q, 3H), (Isomer 4): −79.09 (q, 3H), −77.65 (q, 3H)

GC-MS (EI): (Isomer 1): m/e 374 (M+), 359, 314, 305 (—CF3), 288, (Isomer2): m/e 374 (M+), 359, 333, 316, 305 (—CF3), (Isomer 3): m/e 374 (M+),356 (—H2O), 305 (—CF3), 288, (Isomer 4): m/e 374 (M+), 356 (—H2O), 305(—CF3), 288

Example 7 Synthesis of Polymer Compound 8

A 100 ml round-bottom flask equipped with a reflux condenser and astirrer was charged with the compound 2 (12.1 g), t-butylα-trifluoromethylacrylate (7.9 g), azobisisobutyronitrile (AIBN) (0.44g), and n-butyl acetate (1.0 ml), followed by replacing the inside ofthe flask with nitrogen. This was heated in an oil bath of 60° C., andstirring was conducted for 18 hours. After the reaction, it was added ton-hexane (600 ml), followed by stirring. The resulting precipitate wastaken out. This was dried at 55° C. for 18 hours, thereby obtaining thepolymer compound 8 (9.6 g) of a white-color solid. The molecular weightwas determined from GPC (standard polystyrene). The results are shown inTable 1.

Example 8 Synthesis of Polymer Compound 9

A 50 ml round-bottom flask equipped with a reflux condenser and astirrer was charged with the compound 3 (1.5 g), t-butylα-trifluoromethylacrylate (1.0 g), AIBN (0.20 g), and n-butyl acetate(1.0 ml), followed by replacing the inside of the flask with nitrogen.This was heated in an oil bath of 60° C., and stirring was conducted for18 hours. After the reaction, it was added to n-hexane (120 ml),followed by stirring. The resulting precipitate was taken out. This wasdried at 55° C. for 18 hours, thereby obtaining the polymer compound 9(1.3 g) of a white-color solid. The molecular weight was determined fromGPC (standard polystyrene). The results are shown in Table 1.

Example 9 Synthesis of Polymer Compound 10

A 300 ml round-bottom flask equipped with a reflux condenser and astirrer was charged with the compound 7 (10.0 g),methyladamantylmethacrylate (6.3 g), AIBN (0.35 g), methyl ethyl ketone(82 ml) and n-dodecylmercaptane (0.22 g), followed by replacing theinside of the flask with nitrogen. This was heated in an oil bath of 70°C., and stirring was conducted for 18 hours. After the reaction, it wasadded to n-hexane (600 ml), followed by stirring. The resultingprecipitate was taken out. This was dried at 55° C. for 18 hours,thereby obtaining the polymer compound 10 (11.7 g) of a white-colorsolid. The molecular weight was determined from GPC (standardpolystyrene). The results are shown in Table 1.

Example 10 Synthesis of Polymer Compounds 11 and 12

A 300 ml round-bottom flask equipped with a reflux condenser and astirrer was charged with the compound 7 (10.0 g), AIBN (0.18 g), methylethyl ketone (50 ml) and n-dodecylmercaptane (0.11 g), followed byreplacing the inside of the flask with nitrogen. This was heated in anoil bath of 70° C., and stirring was conducted for 18 hours. After thereaction, it was added to n-hexane (430 ml), followed by stirring. Theresulting precipitate was taken out. This was dried at 55° C. for 18hours, thereby obtaining the polymer compound 11 (8.7 g) of awhite-color solid. The molecular weight was determined from GPC(standard polystyrene). The results are shown in Table 1.

Then, a 100 ml round-bottom flask equipped with a reflux condenser and astirrer was charged with the polymer compound 11 (2.0 g) and dehydratedtetrahydrofuran (30 ml) to dissolve it. The inside of the flask wasturned into nitrogen atmosphere, followed by cooling with ice, addingNaH (0.16 g) and stirring for 30 min. Furthermore, stirring wasconducted at room temperature for 1 hr, followed by adding chloromethylmethyl ether (MOMCl) (0.43 g) and stirring at room temperature for 1 hr.After the reaction, the solution was added to a mixed solvent of waterand methanol (1:1 by volume, 200 ml). The resulting precipitate was wellwashed with water. The obtained white-color solid was dissolved inacetone (10 ml), followed by filtration. The filtrate was added ton-hexane (200 ml), followed by stirring. The resulting precipitate wastaken out. This was dried at 55° C. for 18 hours, thereby obtaining thepolymer compound 12 (1.6 g) of a white-color solid. The molecular weightwas determined from GPC (standard polystyrene). The results are shown inTable 1.

Example 11 Synthesis of Polymer Compound 13

A 500 ml round-bottom flask equipped with a reflux condenser and astirrer was charged with the compound 7 (10.0 g),ethyladamantylmethacrylate (6.4 g), MA-3,5-HFA-CHOH (3.6 g), AIBN (0.53g), methyl ethyl ketone (148 ml) and n-dodecylmercaptane (0.33 g),followed by replacing the inside of the flask with nitrogen. This washeated in an oil bath of 70° C., and stirring was conducted for 18hours. After the reaction, it was added to n-hexane (900 ml), followedby stirring. The resulting precipitate was taken out. This was dried at55° C. for 18 hours, thereby obtaining the polymer compound 13 (17.2 g)of a white-color solid. The molecular weight was determined from GPC(standard polystyrene). The results are shown in Table 1.

Example 12 Synthesis of Polymer Compound 14

A 500 ml round-bottom flask equipped with a reflux condenser and astirrer was charged with the compound 7 (7.8 g),methyladamantylmethacrylate (4.9 g), MA-2-HFA-CHOH (4.7 g), norbornanelactone methacrylate (3.1 g), AIBN (0.51 g), methyl ethyl ketone (128ml) and n-dodecylmercaptane (0.30 g), followed by replacing the insideof the flask with nitrogen. This was heated in an oil bath of 70° C.,and stirring was conducted for 18 hours. After the reaction, it wasadded to n-hexane (800 ml), followed by stirring. The resultingprecipitate was taken out. This was dried at 55° C. for 18 hours,thereby obtaining the polymer compound 14 (16.6 g) of a white-colorsolid. The molecular weight was determined from GPC (standardpolystyrene). The results are shown in Table 1.

TABLE 1 Formed Molecular Weight Ex. Charged Monomers, etc. Polymer YieldMw (Mw/Mn) 7 Compound 2 12.1 g Polymer 8 8.0 g  6,400 (1.42) t-butylα-trifluoromethylacrylate 7.9 g 8 Compound 3 1.5 g Polymer 9 1.2 g 7,000 (1.36) t-butyl α-trifluoromethylacrylate 1.0 g 9 Compound 7 10.0g Polymer 10 11.7 g  10,200 (1.64) methyladamantylmethacrylate 6.3 g 10Compound 7 10.0 g Polymer 11 8.7 g 16,500 (1.38) 10 Polymer 11 2.0 gPolymer 12 1.6 g 16,600 (1.37) 11 Compound 7 10.0 g Polymer 13 17.2 g 14,900 (1.55) ethyladamantylmethacrylate 6.4 g MA-3,5-HFA-CHOH 13.3 g 12Compound 7 7.8 g Polymer 14 16.6 g  12,300 (1.51)methyladamantylmethacrylate 4.9 g MA-2-HFA-CHOH 4.7 g norbornane lactonemethacrylate 3.1 g

Example 13

The polymer compounds 8 to 14 of Examples 7-12 were each dissolved inpropylene glycol methyl acetate, and they were adjusted to a solidmatter portion of 14%. Furthermore, triphenylsulfonium triflate (TPS105)made by Midori Kagaku Co., Ltd. as an acid generator was dissolved in amanner to be 2 parts by weight per 100 parts by weight of the polymercompound, thereby preparing resist solutions. These were subjected tospin coating. By a measurement of light transmittance of a filmthickness of 250 nm at a wavelength of 193 nm, they were 75.0%, 74.9%,68.8%, 74.0%, 72.5%, 73.1%, and 70.6% in the order of polymer compounds8, 9, 10, 11, 12, 13, and 14, showing high transparency in ultravioletregion.

Then, all of the resist solutions were filtered with a membrane filer ofa pore diameter of 0.2 μm. Then, each composition solution was appliedto a silicon wafer by spin coating to obtain a resist film of a filmthickness of 250 nm. After conducting a preliminary baking at 120° C.,an exposure to a 248 nm ultraviolet ray was conducted through aphotomask. Then, a post exposure baking was conducted at 120° C. Then, adevelopment was conducted at 22° C. for 1 minute using 2.38 wt %tetramethylammonium hydroxide aqueous solution. As a result, ahigh-resolution pattern was obtained from each resist solution. Therewere almost not found inferiority defect in adhesion to substrate,film-forming inferiority defect, development defect, and etchingresistance inferiority defect.

1. A fluorine-containing cyclic compound represented by the followinggeneral formula (1):

in the general formula (1), R1a is a C₁-C₂₅ cyclic alkyl group, cyclicalkenyl group or cyclic alkynyl group; each of R2 and R3 isindependently a hydrogen atom, a halogen atom, or a C₁-C₂₅straight-chain, branched or cyclic alkyl group; and each of R1a, R2 andR3 may contain fluorine atom, oxygen atom, sulfur atom, nitrogen atom oran atomic group containing a carbon-carbon double bond.
 2. Afluorine-containing cyclic compound represented by the following generalformula (2):

in the general formula (2), R1a is a C₁-C₂₅ cyclic alkyl group, cyclicalkenyl group or cyclic alkynyl group; each of R2 to R4 is independentlya hydrogen atom, a halogen atom, or a C₁-C₂₅ straight-chain, branched orcyclic alkyl group; and each of R1a and R2 to R4 may contain fluorineatom, oxygen atom, sulfur atom, nitrogen atom or an atomic groupcontaining a carbon-carbon double bond.
 3. A fluorine-containing cycliccompound represented by the following general formula (4):

in the general formula (4), each of R2, R3 and R9 to R15 isindependently a hydrogen atom, a halogen atom, or a C₁-C₂₅straight-chain, branched or cyclic alkyl group, and may contain fluorineatom, oxygen atom, sulfur atom, or nitrogen atom; R10 and R11 or R12 andR13 may be bonded together to form a ring; in such case, it is an C₁-C₂₅alkylene group that may contain oxygen, sulfur, nitrogen or hetero atom;and “a” is 0 or 1, “b” is an integer of 0-2, and “c” is an integer of0-2.
 4. A fluorine-containing cyclic compound represented by thefollowing general formula (5):

in the general formula (5), each of R2 to R4 and R9 to R15 isindependently a hydrogen atom, a halogen atom, or a C₁-C₂₅straight-chain, branched or cyclic alkyl group, and may contain fluorineatom, oxygen atom, sulfur atom, or nitrogen atom; R10 and R11 or R12 andR13 may be bonded together to form a ring; in such case, it is an C₁-C₂₅alkylene group that may contain oxygen, sulfur, nitrogen or hetero atom;and “a” is 0 or 1, “b” is an integer of 0-2, and “c” is an integer of0-2.
 5. A fluorine-containing cyclic compound represented by thefollowing general formula (7):

in the general formula (7), each of R2 and R3 is independently ahydrogen atom, a halogen atom, or a C₁-C₂₅ straight-chain, branched orcyclic alkyl group, and may contain fluorine atom, oxygen atom, sulfuratom, or nitrogen atom.
 6. A fluorine-containing cyclic compoundrepresented by the following general formula (8):

in the general formula (8), each of R2 to R4 is independently a hydrogenatom, a halogen atom, or a C₁-C₂₅ straight-chain, branched or cyclicalkyl group, and may contain fluorine atom, oxygen atom, sulfur atom, ornitrogen atom.
 7. A fluorine-containing polymer compound having a weightaverage molecular weight of 1,000 to 1,000,000, which is characterizedin comprising a repeating unit represented by the following generalformula (13):

in the general formula (13), R2, R3 and R9 to R15 and a, b and c aredefined as in claim
 3. 8. A fluorine-containing polymer compound havinga weight average molecular weight of 1,000 to 1,000,000, which ischaracterized in comprising a repeating unit represented by thefollowing general formula (14):

in the general formula (14), R2 to R4 and R9 to R15 and a, b and c aredefined as in claim
 4. 9. A fluorine-containing polymer compound havinga weight average molecular weight of 1,000 to 1,000,000, which ischaracterized in comprising a repeating unit represented by thefollowing general formula (15):

in the general formula (15), R2 and R3 are defined as in claim
 5. 10. Afluorine-containing polymer compound having a weight average molecularweight of 1,000 to 1,000,000, which is characterized in comprising arepeating unit represented by the following general formula (16):

in the general formula (16), R2 to R4 are defined as in claim
 6. 11. Afluorine-containing polymer compound having a weight average molecularweight of 1,000 to 1,000,000 according to claim 7, which comprises arepeating unit represented by the following general formula (17):

in the general formula (17), R16 is a hydrogen atom, or a C₁-C₂₅straight-chain, branched or cyclic alkyl group, and may contain fluorineatom, oxygen atom, sulfur atom, nitrogen atom, hydroxyl group orhexafluorocarbinol group.
 12. A fluorine-containing cyclic compoundaccording to claim 1, wherein hydroxy groups contained in the moleculeare partially or entirely protected with protecting groups.